CN113223767B - Anti-corrosion acid and alkali resistant watertight cable and preparation method thereof - Google Patents
Anti-corrosion acid and alkali resistant watertight cable and preparation method thereof Download PDFInfo
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- CN113223767B CN113223767B CN202110334942.3A CN202110334942A CN113223767B CN 113223767 B CN113223767 B CN 113223767B CN 202110334942 A CN202110334942 A CN 202110334942A CN 113223767 B CN113223767 B CN 113223767B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
- H01B7/2806—Protection against damage caused by corrosion
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
- H01B7/282—Preventing penetration of fluid, e.g. water or humidity, into conductor or cable
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
- H01B7/282—Preventing penetration of fluid, e.g. water or humidity, into conductor or cable
- H01B7/285—Preventing penetration of fluid, e.g. water or humidity, into conductor or cable by completely or partially filling interstices in the cable
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Abstract
The invention discloses an anti-corrosion acid and alkali resistant watertight cable and a preparation method thereof, and relates to the technical field of cables. According to the anti-corrosion acid and alkali resistant watertight cable, the multistage water-blocking layers are arranged on the structure and are tightly filled, the water-blocking effect is good, and the chloroprene rubber is used as the base material of the outer sheath, so that the anti-corrosion acid and alkali resistant watertight cable is good in anti-corrosion and acid and alkali resistant effects and can be used in deep sea water environments.
Description
Technical Field
The invention relates to the technical field of cables, in particular to an anti-corrosion acid and alkali resistant watertight cable, a preparation method thereof and application thereof in watertight cables.
Background
In recent years, the scale of the ship industry in China is rapidly enlarged, the yield of ships is rapidly increased, the varieties and structures of the ships are continuously upgraded, and the leap-type development of ship corollary equipment in China is imperative. The watertight cable is a cable with longitudinal water resistance for underwater ships or devices, and at present, the cable for meeting the requirement of major ocean engineering depends on foreign import, the key technology of the watertight cable is monopolized by foreign countries, and the domestic autonomous development technology has a large gap with the foreign advanced level.
In order to play a role of water resistance, the existing watertight cable is often only provided with a layer of water resistant layer on the outer layer of the cable, for example, the prior patent number is 201910773946.4, which is a Chinese invention patent named as 'a watertight cable and a manufacturing method thereof', which is to extrude a watertight sheath layer outside a cable isolating layer to achieve the effect of water resistance, such an arrangement provides a low level of water blocking, which can have significant consequences in the event of failure of the outer layer, in the prior art, some watertight cables are added with water-blocking tapes, water-blocking yarns and the like to achieve the water-blocking effect when conductors are twisted, however, the method cannot effectively fill gaps among the conductors, watertight failure can be caused, and the conductors are affected by the uneven and weak electric conductivity of the water blocking tape or the water blocking yarn, so that a new watertight cable suitable for deep water needs to be designed.
Disclosure of Invention
In order to solve the problems, the invention aims to provide the corrosion-resistant, acid-resistant and alkali-resistant watertight cable and the preparation method thereof.
The invention solves the technical problems through the following technical means:
the utility model provides an anticorrosion acid and alkali-resistance watertight cable, the cable includes many electrically conductive central unit, many electrically conductive central unit transposition stranding, and the space department between the electrically conductive central unit all fills and blocks water glues formation middle water blocking layer, many the outer cladding of electrically conductive central unit has the polyester layer, metal shielding layer and oversheath have set gradually outward to the polyester layer, be provided with outer water blocking layer between oversheath and the metal shielding layer.
Furthermore, the conductive central unit comprises a plurality of stranded conductors and insulating layers wrapped outside the conductors, and a semi-conductive water-blocking glue is filled between the conductors to form an internal water-blocking layer.
The watertight cable is provided with the inner water-blocking layer, the middle water-blocking layer and the outer water-blocking layer, the water-blocking effect of the watertight cable is structurally improved, an inner conductor can be better blocked, all the water-blocking layers are formed by coating or filling water-blocking glue, no gap exists between the conductor and the conductor, and the water-blocking effect is more stable by combining the semi-conductive water-blocking glue.
Further, the metal shielding layer is formed by weaving annealed copper wires, and the weaving density is 82% -83%.
Further, the outer sheath comprises the following raw materials in parts by weight: 40-60 parts of chloroprene rubber, 20-25 parts of modified polytetrafluoroethylene, 16-18 parts of polyamide, 2-8 parts of nano silicon nitride, 3-5 parts of carbon nano fiber, 1-2 parts of zinc oxide, 1-2 parts of higher fatty alcohol, 0.5-1 part of calcium stearate and 3-4 parts of processing aid.
The outer sheath adopts chloroprene rubber and modified polytetrafluoroethylene as main bodies, has good corrosion resistance and acid and alkali resistance, so that the watertight cable can better adapt to a seawater environment and prolong the service life of the watertight cable, and the nano silicon nitride and the carbon nanofiber can improve the mechanical property and the mechanical property of the matrix material, so that the watertight cable can adapt to a deepwater environment, resist water pressure and protect an internal conductor from normal work.
Furthermore, the modified polytetrafluoroethylene is prepared by compositely modifying polytetrafluoroethylene by tannic acid and trimesoyl chloride.
The interfacial polymerization reaction of tannic acid and trimesoyl chloride on the surface of the polytetrafluoroethylene is carried out, chlorine is introduced on the polytetrafluoroethylene, and the polarity of the polytetrafluoroethylene is increased, so that the compatibility between the polytetrafluoroethylene and chloroprene rubber is improved.
Further, the semi-conductive water-resistant adhesive comprises the following raw materials: the composite conductive silicon rubber comprises two components of silicon rubber, silicon resin, composite conductive particles, chlorinated paraffin, 2-3 parts of N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
Further, the semiconductor water-resistant adhesive comprises the following raw materials in parts by weight: 100 parts of double-component silicon rubber, 20-28 parts of silicon resin, 10-16 parts of composite conductive particles, 4-6 parts of chlorinated paraffin, 2-3 parts of N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane and 1-2 parts of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
Furthermore, the composite conductive particles are core-shell structures which take CoP quantum dot/conductive carbon black composite particles as cores and are wrapped with polyaniline shells.
According to the composite conductive particle, CoP quantum dots and conductive carbon black are compounded, the CoP quantum dots can be uniformly combined to provide more active interfaces for the conductive carbon black, the electronic conduction between polyaniline and the conductive active carbon can be promoted, and then the CoP quantum dots/the conductive carbon black composite particles are wrapped by the polyaniline, so that on one hand, a polyaniline shell layer can interact with the internal conductive carbon black to improve the integral conductive property, on the other hand, the polyaniline shell layer can reduce the agglomeration effect between the conductive carbon black composite particles and improve the compatibility between the conductive carbon black and silicon rubber of a base body, so that the CoP quantum dots/the conductive carbon black composite particles are uniformly distributed in the base body material to form a stable conductive network, the conductivity of a semiconductor water-blocking adhesive is further improved, and the polyaniline of the shell layer can also play a certain limiting role on the CoP quantum dots/the conductive carbon black composite particles to a certain extent in the using process The stability of the water-blocking adhesive is guaranteed, and in addition, through the research of the inventor, the optimal addition amount is obtained, so that the conductivity of the water-blocking adhesive for the semiconductor is not influenced by overhigh or overlow conductivity.
Further, the preparation method of the composite conductive particles comprises the following steps:
preparation of CoP quantum dot/conductive carbon black composite particles: dissolving cobalt nitrate and 2-methylimidazole in distilled water in sequence, adding pretreated conductive carbon black powder, standing for 4-6 hours, taking out the conductive carbon black powder, placing the conductive carbon black powder in a quartz boat, placing sodium hypophosphite in another quartz boat, placing the quartz boat at the upstream of the conductive carbon black powder, calcining for 2 hours at 400 ℃ in an argon atmosphere, cooling to room temperature, and taking out to obtain CoP quantum dot/conductive carbon black composite particles;
preparing the composite conductive particles: stirring and dispersing the prepared CoP quantum dot/conductive carbon black composite particles in deionized water, adding aniline, performing ultrasonic dispersion uniformly, adding concentrated hydrochloric acid at the temperature of 0-4 ℃, stirring and reacting for 10min, adding a manganese dioxide solution, continuing to react for 10-15min, dropwise adding an ammonium persulfate solution, continuously stirring and reacting for 4h, filtering, soaking a filter cake in 1mol/L ammonia water solution for 12h, cleaning with an ethanol solution after filtering, and performing vacuum drying to obtain the composite conductive particles.
Further, the pretreatment of the conductive carbon black powder specifically comprises the following steps: stirring and dispersing conductive carbon black powder in a mixed acid solution, soaking for 12-16h, performing ultrasonic oscillation once every 4h, filtering after the treatment is finished, drying a filter cake, performing heat treatment at 800 ℃ for 4h in an oxygen-enriched atmosphere, cooling along with a furnace, taking out, stirring and dispersing in an ethanol solution, adding polyethylene pyrrolidone, stirring and uniformly mixing, adding methyl methacrylate and azodiisobutyronitrile, heating to 80 ℃ in a nitrogen atmosphere, controlling the reaction time, filtering after the reaction is finished, washing the filter cake with absolute ethyl alcohol for three times, and drying.
The preparation method comprises the steps of pretreating conductive carbon black powder, activating the conductive carbon black powder by using a mixed acid solution and heat treatment, increasing oxygen-containing groups on the conductive carbon black powder, then forming polymethyl methacrylate on the conductive carbon black powder in situ by using polyethylene pyrrolidone as a dispersing agent, increasing the surface roughness of the conductive carbon black powder, and introducing functional groups such as hydroxyl, carbonyl, carboxyl and the like on the nano conductive carbon powder, so that favorable conditions are provided for the subsequent compounding of CoP quantum dots.
Further, the mixed acid solution is a mixed solution of nitric acid and sulfuric acid, and the volume ratio of the nitric acid to the sulfuric acid in the mixed acid solution is 3: 1.
Further, the preparation method of the semiconductor water-resistant adhesive comprises the following steps: heating the temperature of a kneader to 140-150 ℃, adding two-component silicon rubber, banburying for 20min, adding the silicon resin, keeping the temperature for 45-50min, cooling to 110-120 ℃, adding chlorinated paraffin, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, stirring and mixing uniformly, cooling to 80-90 ℃, adding composite conductive particles, stirring and mixing for 60min, standing and defoaming in vacuum, cooling and continuously stirring for 1h under the vacuum condition, and discharging to obtain the semiconductor water-blocking adhesive
In addition, the invention also discloses a preparation method of the anti-corrosion acid and alkali resistant watertight cable, which specifically comprises the following steps:
stranding: twisting a plurality of required conductors, coating semiconductor water-blocking glue on the conductors while twisting, filling the semiconductor water-blocking glue in gaps among the conductors, and obtaining an internal water-blocking layer after solidification;
insulation: extruding an insulating layer on the surfaces of the conductors to obtain a conductive central unit;
cabling: taking the required conductive central units, stranding and cabling in a right cabling direction in a layered stranding mode, simultaneously lapping polyester tapes on the outer sides of the plurality of conductive central units in a left overlapping mode to form polyester layers, and filling water-blocking glue behind each stranding cage in the stranding process to form a middle water-blocking layer;
weaving a metal shielding layer: weaving a soft copper wire outside the polyester layer to obtain a metal shielding layer, and coating a water-blocking adhesive on the metal shielding layer to form an outer water-blocking layer;
molding: and extruding and coating the smelted outer sheath raw material outside the outer water-blocking layer by using an extruding machine to obtain the watertight cable.
Further, the refining of the raw materials of the outer sheath specifically comprises the following steps: putting nano silicon nitride, carbon nanofiber and zinc oxide into a ball mill, ball-milling and uniformly mixing for 30-40min, adding absolute ethyl alcohol, carrying out ultrasonic oscillation for 10min, centrifuging and drying to obtain mixed granules, adding chloroprene rubber, modified tetrafluoroethylene and polyamide into an internal mixing furnace, heating to 150-180 ℃ within 30-45s, carrying out internal mixing for 30min, heating to 240-260 ℃ within 45-60s, carrying out internal mixing for 45min, cooling to 100-105 ℃ within 120-150s, adding the mixed granules, carrying out mixing for 20-30min, adding higher fatty alcohol, calcium stearate and processing aids, heating to 135-150 ℃, and carrying out internal mixing for 10-15min, and discharging.
Further, the preparation method of the modified polytetrafluoroethylene comprises the following steps: adding sodium bicarbonate into deionized water, stirring to dissolve completely, adding Tween 80, stirring uniformly, adding tannic acid, magnetically stirring until the sodium bicarbonate is dissolved completely to obtain a tannic acid mixed solution, weighing trimesoyl chloride, adding the trimesoyl chloride into a normal hexane solution, carrying out ultrasonic oscillation for 30min, standing to remove bubbles to obtain a trimesoyl chloride mixed solution, cleaning polytetrafluoroethylene with deionized water and absolute ethyl alcohol in sequence, drying, adding the cleaned polytetrafluoroethylene into the tannic acid mixed solution, soaking for 15min, taking out the polytetrafluoroethylene, immediately adding the cleaned polytetrafluoroethylene into the trimesoyl chloride solution, carrying out stirring reaction for 5min, centrifuging, drying with hot air, baking at the temperature of 60 ℃ for 30min, taking out the dried polytetrafluoroethylene, cleaning with deionized water, and drying.
The invention has the beneficial effects that:
1. according to the anti-corrosion acid and alkali resistant watertight cable, the multistage water-blocking layers are arranged on the structure and are tightly filled, the water-blocking effect is good, and the chloroprene rubber is used as the base material of the outer sheath, so that the anti-corrosion acid and alkali resistant watertight cable is good in anti-corrosion and acid and alkali resistant effects and can be used in deep sea water environments.
2. The semiconductor water-blocking adhesive disclosed by the invention is good in adhesive force, the used composite conductive particles are better in compatibility with a silicon rubber matrix, the influence on the processability of the silicon rubber matrix is smaller, and the composite conductive particles can be uniformly dispersed in the silicon rubber matrix to form a stable conductive network, so that the conductive performance of the semiconductor water-blocking adhesive is more stable.
Drawings
FIG. 1 is a schematic structural diagram of the corrosion-resistant acid and alkali-resistant watertight cable of the present invention;
the cable comprises a conductor 11, an insulating layer 12, an inner water-resistant layer 13, an intermediate water-resistant layer 2, a polyester layer 3, a metal shielding layer 4, an outer sheath 5 and an outer water-resistant layer 6.
Detailed Description
The present invention will be described in detail below with reference to specific examples:
the invention relates to an anticorrosion acid and alkali resistant watertight cable, which comprises a plurality of conductive central units, wherein each conductive central unit comprises a plurality of stranded conductors 11 and insulating layers 12 wrapping the plurality of conductors, semiconductive water-blocking glue is filled among the plurality of conductors to form an inner water-blocking layer 13, the plurality of conductive central units are stranded into a cable, water-blocking glue is filled in gaps among the conductive central units to form a middle water-blocking layer 2, polyester layers 3 are coated outside the plurality of conductive central units, metal shielding layers 4 and outer sheaths 5 are sequentially arranged outside the polyester layers 3, and outer water-blocking layers 6 are arranged between the outer sheaths 5 and the metal shielding layers 4.
The semiconductor water-blocking adhesive uses composite conductive particles in raw materials, the composite conductive particles take CoP quantum dot/conductive carbon black composite particles as cores, and a core-shell structure with polyaniline shells is wrapped outside the cores, and the semiconductor water-blocking adhesive specifically comprises the following components:
EXAMPLES preparation of a Water-blocking adhesive for semiconductor 1
Pretreatment of conductive carbon black powder
Stirring and mixing concentrated nitric acid and concentrated sulfuric acid according to the volume ratio of 3:1 to obtain a mixed acid solution, weighing conductive carbon black powder, stirring and dispersing the conductive carbon black powder in the mixed acid solution, soaking for 12-16h, carrying out ultrasonic oscillation once every 4h, filtering after the treatment is finished, drying a filter cake, carrying out heat treatment for 4h at the temperature of 800 ℃ in an oxygen-rich atmosphere, cooling along with a furnace, taking out, stirring and dispersing the conductive carbon black powder in a 65 wt% ethanol solution according to the solid-to-liquid ratio of 1g/L, adding 3% times of polyvinylpyrrolidone based on the mass of the conductive carbon black powder, stirring and uniformly mixing, adding methyl methacrylate and azodiisobutyronitrile, keeping the mass ratio of the conductive carbon black powder to the methyl methacrylate to the azodiisobutyronitrile to be 1:0.5:0.005, heating to 80 ℃ in a nitrogen atmosphere, controlling the reaction time to be 6h, filtering after the reaction is finished, washing the filter cake for three times by using absolute ethanol, and (5) drying.
Preparation of composite conductive particles
Preparing CoP quantum dot/conductive carbon black composite particles: dissolving cobalt nitrate and 2-methylimidazole in distilled water with the mass ratio of 1:2 of 80 times of the mass of the cobalt nitrate in sequence, then adding 1/2 times of pretreated conductive carbon black powder with the mass of the cobalt nitrate, standing for 6 hours, taking out the conductive carbon black powder, placing the conductive carbon black powder in a quartz boat, placing sodium hypophosphite with the mass of 4 times of the conductive carbon black powder in another quartz boat, placing the quartz boat at the upstream of the conductive carbon black powder, calcining for 2 hours at 400 ℃ in an argon atmosphere, cooling to room temperature, and taking out to obtain CoP quantum dot/conductive carbon black composite particles;
preparing the composite conductive particles: stirring and dispersing the prepared CoP quantum dot/conductive carbon black composite particles in deionized water according to a solid-to-liquid ratio of 1g/L, adding aniline of 12 times the mass of the CoP quantum dot/conductive carbon black composite particles, uniformly dispersing by ultrasonic, adding concentrated hydrochloric acid of 0.1 time of the volume of the deionized water at the temperature of 0-4 ℃, stirring and reacting for 10min, adding a 5 wt% manganese dioxide solution of equal volume of the concentrated hydrochloric acid, continuously reacting for 12min, dropwise adding 100mg/mL ammonium persulfate solution of 1.5 times of the volume of the concentrated hydrochloric acid at the speed of 1-2d/s, continuously stirring and reacting for 4h, filtering, soaking a filter cake in 1mol/L ammonia water solution for 12h, cleaning by using an ethanol solution after filtering, and vacuum drying at the temperature of 60 ℃ to obtain the composite conductive particles.
Preparation of semiconductor water-resistant glue
The preparation method comprises the following steps: heating a kneader to 150 ℃, adding 100 parts by weight of double-component silicone rubber, banburying for 20min, adding 28 parts by weight of silicone resin, keeping the temperature for 50min, cooling to 110 ℃, adding 6 parts by weight of chlorinated paraffin, 3 parts by weight of N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane and 1 part by weight of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, uniformly stirring and mixing, cooling to 90 ℃, adding 16 parts by weight of composite conductive particles, stirring and mixing for 60min, standing and defoaming in vacuum, cooling and continuously stirring for 1h under the vacuum condition, and discharging to obtain the semiconductor water-blocking adhesive.
EXAMPLE 2 preparation of semiconductor Water-blocking adhesive
The pretreatment of the conductive carbon black powder was the same as in example one.
Preparation of composite conductive particles
Preparing CoP quantum dot/conductive carbon black composite particles: dissolving cobalt nitrate and 2-methylimidazole in distilled water 90 times of the mass of the cobalt nitrate according to the mass ratio of 1:3, then adding 1/2 times of pretreated conductive carbon black powder of the mass of the cobalt nitrate, standing for 5 hours, taking out the conductive carbon black powder, placing the conductive carbon black powder in a quartz boat, placing sodium hypophosphite 4 times of the mass of the conductive carbon black powder in another quartz boat, placing the quartz boat at the upstream of the conductive carbon black powder, calcining for 2 hours at 400 ℃ in an argon atmosphere, cooling to room temperature, and taking out to obtain CoP quantum dot/conductive carbon black composite particles;
preparing the composite conductive particles: stirring and dispersing the prepared CoP quantum dot/conductive carbon black composite particles in deionized water according to a solid-liquid ratio of 1.2g/L, adding aniline of 8 times the mass of the CoP quantum dot/conductive carbon black composite particles, uniformly dispersing by ultrasonic, adding concentrated hydrochloric acid of 0.1 time of the volume of the deionized water at the temperature of 0-4 ℃, stirring and reacting for 10min, adding a 5 wt% manganese dioxide solution of equal volume of the concentrated hydrochloric acid, continuously reacting for 15min, dropwise adding a 100mg/mL ammonium persulfate solution of 1.5 times of the volume of the concentrated hydrochloric acid at the speed of 1-2d/s, continuously stirring and reacting for 4h, filtering, soaking a filter cake in 1mol/L ammonia water solution for 12h, cleaning by using an ethanol solution after filtering, and drying in vacuum at the temperature of 60 ℃ to obtain the composite conductive particles.
Preparation of semiconductor water-blocking glue
The preparation method comprises the following steps: heating a kneader to 150 ℃, adding 100 parts by weight of double-component silicone rubber, banburying for 20min, adding 26 parts by weight of silicone resin, keeping the temperature for 45min, cooling to 20 ℃, adding 5 parts by weight of chlorinated paraffin, 2 parts by weight of N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane and 1 part by weight of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, uniformly stirring and mixing, cooling to 85 ℃, adding 13 parts by weight of composite conductive particles, stirring and mixing for 60min, standing and defoaming in vacuum, cooling and continuously stirring for 1h under the vacuum condition, and discharging to obtain the semiconductor water-blocking adhesive.
EXAMPLE III preparation of semiconductor Water-blocking adhesive 3
The pretreatment of the conductive carbon black powder was the same as in example one.
Preparation of composite conductive particles
Preparing CoP quantum dot/conductive carbon black composite particles: dissolving cobalt nitrate and 2-methylimidazole in distilled water 100 times of the mass of the cobalt nitrate according to a mass ratio of 1:2 in sequence, then adding 1/3 times of pretreated conductive carbon black powder by mass of the cobalt nitrate, standing for 4 hours, fishing out the conductive carbon black powder, placing the conductive carbon black powder in a quartz boat, placing sodium hypophosphite 4 times of the mass of the conductive carbon black powder in another quartz boat, placing the quartz boat at the upstream of the conductive carbon black powder, calcining for 2 hours at 400 ℃ in an argon atmosphere, cooling to room temperature, and taking out to obtain CoP quantum dot/conductive carbon black composite particles;
preparing the composite conductive particles: stirring and dispersing the prepared CoP quantum dot/conductive carbon black composite particles in deionized water according to a solid-to-liquid ratio of 1.1g/L, adding aniline of which the mass is 10 times that of the CoP quantum dot/conductive carbon black composite particles, ultrasonically dispersing uniformly, adding concentrated hydrochloric acid of which the volume is 0.1 time that of the deionized water at the temperature of 0-4 ℃, stirring and reacting for 10min, adding a manganese dioxide solution of which the volume is 5 wt% of that of the concentrated hydrochloric acid, continuously reacting for 15min, dropwise adding 100mg/mL ammonium persulfate solution of which the volume is 1.5 times that of the concentrated hydrochloric acid at the speed of 1-2d/s, continuously stirring and reacting for 4h, filtering, soaking a filter cake in 1mol/L ammonia water solution for 12h, cleaning by using an ethanol solution after filtering, and vacuum drying at the temperature of 60 ℃ to obtain the composite conductive particles.
Preparation of semiconductor water-resistant glue
The preparation method comprises the following steps: heating the temperature of a kneader to 145 ℃, adding 100 parts by weight of double-component silicone rubber, banburying for 20min, adding 20 parts by weight of silicone resin, keeping the temperature for 50min, cooling to 115 ℃, adding 4 parts by weight of chlorinated paraffin, 2 parts by weight of N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane and 2 parts by weight of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, uniformly stirring and mixing, cooling to 80 ℃, adding 10 parts by weight of composite conductive particles, stirring and mixing for 60min, standing and defoaming in vacuum, cooling and continuously stirring for 1h under the vacuum condition, and discharging to obtain the semiconductor water-blocking adhesive.
Example preparation of four Watertight cables 1
Preparing modified polytetrafluoroethylene: respectively weighing sodium bicarbonate, tannic acid and tween 80 according to a mass ratio of 1.2:1:0.1, adding the sodium bicarbonate into deionized water, stirring to completely dissolve the sodium bicarbonate, adding the tween 80, stirring to uniformly mix, adding the tannic acid, magnetically stirring to completely dissolve the sodium bicarbonate to obtain a tannic acid mixed solution of 2.5 wt%, weighing trimesoyl chloride, adding the trimesoyl chloride into a normal hexane solution, ultrasonically oscillating for 30min, standing to remove bubbles to obtain a trimesoyl chloride mixed solution of 0.5 wt%, cleaning polytetrafluoroethylene with deionized water and absolute ethyl alcohol in sequence, drying, adding the polytetrafluoroethylene into the tannic acid mixed solution, soaking for 15min, taking out, immediately adding the polytetrafluoroethylene into the trimesoyl chloride solution, stirring to react for 5min, centrifuging, drying with hot air, baking at the temperature of 60 ℃ for 30min, taking out, cleaning with deionized water, and drying for later use.
Refining raw materials of the outer sheath: putting 2 parts by weight of nano silicon nitride, 5 parts by weight of carbon nanofiber and 2 parts by weight of zinc oxide into a ball mill, ball-milling and uniformly mixing for 30min, adding 6 times of volume of absolute ethyl alcohol, ultrasonically oscillating for 10min, centrifuging and drying to obtain mixed granules, adding 50 parts by weight of chloroprene rubber, 25 parts by weight of modified tetrafluoroethylene and 18 parts by weight of polyamide into an internal mixing furnace, heating to 150 ℃ within 30s, internally mixing for 30min, heating to 260 ℃ within 60s, internally mixing for 45min, finally cooling to 105 ℃ within 120s, adding the mixed granules, mixing for 25min, adding 1 part by weight of higher aliphatic alcohol, 0.5 part by weight of calcium stearate and 4 parts by weight of processing aid ACR401, heating to 150 ℃, internally mixing for 12min, and discharging.
Watertight cable preparation
Stranding: taking the nominal sectional area as 1.0mm 2 The multiple conductors are twisted, the twisting direction is left, semiconductor water-blocking glue is coated on the conductors while twisting, so that gaps among the conductors are filled with the semiconductor water-blocking glue, and an internal water-blocking layer is obtained after solidification, wherein the conductors adopt a second type of conductor, and through detection, the outer diameter of a stranded wire obtained after twisting the multiple conductors is 1.30 +/-0.2 mm, the pitch of the stranded wire is 9mm, and the maximum direct current resistance at 20 ℃ is 18.1 omega/km;
insulation: the method comprises the steps of extruding insulating layers on the surfaces of a plurality of conductors to obtain a conductive central unit, wherein the insulating layers are made of existing ethylene-propylene insulating materials, the average thickness of the insulating layers is 0.85mm, the nominal outer diameter of the obtained conductive central unit is 2.91mm, the insulating surface plasticization is good, visual air holes are not formed in the cross section, the conductive central unit is sampled and sent out to be subjected to water tightness detection, the volume of leakage water obtained through detection is 0mL, the displacement is 3.0mm, the water tightness is good, meanwhile, an insulating alternating current voltage test is carried out according to a GB/T3048.4 method, 2kV/5min is applied between a phase and a phase shield, and the insulation is not broken down;
cabling: taking the required conductive central units, stranding and cabling in a right-hand cabling direction in a layered stranding mode, simultaneously lapping polyester tapes outside the plurality of conductive central units in a left-hand overlapping mode to form a polyester layer, ensuring that the average lapping rate is 15% -18% in the lapping process, filling water-blocking glue after each stranding cage at a pitch of 180mm in the stranding process, wherein the water-blocking glue can be the existing water-blocking glue to form a middle water-blocking layer, and the outer diameter obtained after lapping is 15.6 mm;
weaving a metal shielding layer: weaving 7 annealed copper wires with the filament diameter of 0.19mm outside the polyester layer to obtain a metal shielding layer, wherein the weaving density is 82%, coating water-resistant glue on the metal shielding layer to form an outer water-resistant layer, and the outer diameter is 16.5mm after weaving;
molding: extruding and coating the smelted outer sheath raw material outside the outer water blocking layer by using an extruding machine to obtain the watertight cable, and detecting to obtain the watertight cable with the outer diameter of 24mm and the thickness of the outer sheath layer of 3.3 mm.
Example preparation of a five-water-tight Cable 2
The preparation of modified polytetrafluoroethylene was the same as in example four.
Refining raw materials of the outer sheath: putting 8 parts by weight of nano silicon nitride, 4 parts by weight of carbon nanofiber and 1 part by weight of zinc oxide into a ball mill, uniformly mixing for 35min by ball milling, adding 8 times of volume of absolute ethyl alcohol, carrying out ultrasonic oscillation for 10min, centrifuging and drying to obtain mixed granules, adding 40 parts by weight of chloroprene rubber, 20 parts by weight of modified tetrafluoroethylene and 17 parts by weight of polyamide into an internal mixing furnace, heating to 180 ℃ within 45s, carrying out internal mixing for 30min, heating to 250 ℃ within 50s, carrying out internal mixing for 45min, cooling to 100 ℃ within 150s, adding the mixed granules, carrying out internal mixing for 20min, adding 2 parts by weight of higher aliphatic alcohol, 0.5 part by weight of calcium stearate and 3 parts by weight of processing aid ACR401, heating to 145 ℃, carrying out internal mixing for 10min, and discharging.
Watertight cable preparation
Stranding: the nominal sectional area is taken to be 1.0mm 2 Twisting the plurality of conductors, wherein the twisting direction is left direction, coating the semiconductor water-blocking glue on the conductors while twisting, filling the semiconductor water-blocking glue in gaps among the conductors, obtaining an internal water-blocking layer after solidification, and detecting that the outer diameter of a twisted wire obtained after twisting the plurality of conductors is 1.30 +/-0.2 mm, the pitch of the twisted wire is 7mm, and the maximum direct current resistance at 20 ℃ is 17.6 omega/km;
insulation: the method comprises the steps of extruding insulating layers on the surfaces of a plurality of conductors to obtain a conductive center unit, wherein the insulating layers are made of existing ethylene propylene insulating materials, the average thickness of the insulating layers is 0.8mm, the nominal outer diameter of the obtained conductive center unit is 2.91mm, the insulating surfaces are well plasticized, visual air holes are not formed in the cross section, the conductive center unit is sampled and sent out to be subjected to water tightness detection, the volume of leaked water is 0mL through detection, the displacement is 3.5mm, the water tightness is proved to be good, meanwhile, an insulating alternating current voltage test is carried out according to the method of GB/T3048.4, 2kV/5min is applied between a phase and a shield, and the insulation is not broken down;
cabling: taking the required conductive central units, stranding and cabling in a right-hand cabling direction in a layered stranding mode, simultaneously lapping polyester tapes outside the plurality of conductive central units in a left-hand overlapping mode to form a polyester layer, ensuring that the average lapping rate is 18% in the lapping process, filling water-blocking glue behind each stranding cage at a pitch of 190mm in the stranding process, wherein the water-blocking glue at the position can be the existing water-blocking glue to form a middle water-blocking layer, and the outer diameter obtained after lapping is 15.8 mm;
weaving a metal shielding layer: weaving 7 annealed copper wires with the filament diameter of 0.19mm outside the polyester layer to obtain a metal shielding layer, wherein the weaving density is 83%, and meanwhile, coating water-blocking glue on the metal shielding layer to form an outer water-blocking layer, and the outer diameter of the braided metal shielding layer is 16.8 mm;
molding: and extruding and coating the smelted raw material of the outer sheath outside the outer water-blocking layer by using an extruding machine to obtain the watertight cable, and detecting to obtain the watertight cable with the outer diameter of 24mm and the thickness of the outer sheath layer of 3.4 mm.
Example preparation of six Watertight Cable 3
The preparation of modified polytetrafluoroethylene was the same as in example four.
Refining raw materials of the outer sheath: putting 6 parts by weight of nano silicon nitride, 3 parts by weight of carbon nanofiber and 1 part by weight of zinc oxide into a ball mill, uniformly mixing for 40min by ball milling, adding 7 times of volume of absolute ethyl alcohol, carrying out ultrasonic oscillation for 10min, centrifuging and drying to obtain mixed granules, adding 60 parts by weight of chloroprene rubber, 22 parts by weight of modified tetrafluoroethylene and 16 parts by weight of polyamide into an internal mixing furnace, heating to 165 ℃ within 40s, carrying out internal mixing for 30min, heating to 240 ℃ within 45s, carrying out internal mixing for 45min, cooling to 100 ℃ within 130s, adding the mixed granules, carrying out internal mixing for 30min, adding 2 parts by weight of higher aliphatic alcohol, 0.8 part by weight of calcium stearate and 3 parts by weight of processing aid ACR401, heating to 135 ℃, carrying out internal mixing for 15min, and discharging.
Watertight cable preparation
Stranding: taking the nominal sectional area as 1.0mm 2 Twisting the plurality of conductors, wherein the twisting direction is left direction, coating the semiconductor water-blocking glue on the conductors while twisting, filling the semiconductor water-blocking glue in gaps among the conductors, obtaining an internal water-blocking layer after solidification, and detecting that the outer diameter of a twisted wire obtained after twisting the plurality of conductors is 1.30 +/-0.2 mm, the pitch of the twisted wire is 8mm, and the maximum direct current resistance at 20 ℃ is 18.0 omega/km;
insulation: the method comprises the steps of extruding insulating layers on the surfaces of a plurality of conductors to obtain an insulating layer of a conductive center unit, wherein the average thickness of the insulating layer is 0.82mm, the nominal outer diameter of the obtained conductive center unit is 2.91mm, the insulating surface is well plasticized, and the cross section has no visible air holes, sampling and sending out the conductive center unit for water tightness detection, detecting to obtain the volume of leakage water of 0mL and the displacement of 3.2mm, and proving that the water tightness is good, meanwhile, carrying out an insulating alternating current voltage test according to the method of GB/T3048.4, applying 2kV/5min between phase and shielding, and not breaking down the insulation;
cabling: taking the required conductive central units, stranding and cabling in a right-hand cabling direction in a layered stranding mode, simultaneously lapping polyester tapes outside the plurality of conductive central units in a left-hand overlapping mode to form a polyester layer, ensuring that the average lapping rate is 16% in the lapping process, filling water-blocking glue after each stranding cage to form a middle water-blocking layer in the stranding process, wherein the outer diameter obtained after lapping is 15.2 mm;
weaving a metal shielding layer: weaving 7 annealed copper wires with the filament diameter of 0.19mm outside the polyester layer to obtain a metal shielding layer, wherein the weaving density is 82%, and meanwhile, coating water-blocking glue on the metal shielding layer to form an outer water-blocking layer, and the outer diameter is 16.8mm after weaving;
molding: extruding and coating the smelted outer sheath raw material outside the outer water-blocking layer by using an extruding machine to obtain the watertight cable, and detecting to obtain the watertight cable with the outer diameter of 24mm and the thickness of the outer sheath layer of 3.4 mm.
Comparative example 1
The comparative example is different from the first example in that the core of the composite conductive particle of the comparative example is only the pretreated conductive carbon black.
Comparative example No. two
The difference between the present comparative example and the first example is that the composite conductive particle of the present comparative example has only a core and no polyaniline shell layer coated on the outside.
Comparative example No. three
The present comparative example is different from the first example in that the conductive carbon black powder is not pretreated during the preparation of the composite conductive particle of the present comparative example.
Comparative example No. four
This comparative example is different from the first example in that the composite conductive particles of the first example are replaced with conventional conductive carbon black.
The semiconductor water-blocking glue prepared in the first to third embodiments and the first to fourth embodiments is used for testing performances such as colloid strength, volume resistance, waterproofness and the like, and the test results are shown in table 1:
TABLE 1
The data in the table show that the waterproof adhesive has better waterproof performance and more stable conductivity, so that the prepared watertight cable has better waterproof performance.
The watertight performance and the main performance indexes of the watertight cables prepared in the fourth to fifth embodiments are detected, and meanwhile, the watertight cables purchased in the existing market are used for comparison, and the detection results are shown in table 2:
| example four | EXAMPLE five | Example six | Existing cable | |
| Volume of leakage Water/mL | 0 | 0 | 0 | 150 |
| Displacement (end under pressure)/mm | 2.6 | 2.4 | 2.5 | 5.5 |
| Filler slump test (95. + -. 1 ℃ C.) | 0 | 0 | 0 | 0 |
| Elongation at break of the sheath | 300 | 310 | 306 | 247 |
| Cable low temperature bending (-20 ℃ C.) | Without damage | Without damage | Without damage | Micro cracks |
| Fire resistance test 3A fuse | Does not fuse | Does not fuse | Does not fuse | Micro-melting |
As can be seen from the data in Table 2, the water-blocking performance of the watertight cable is far superior to that of the existing watertight cable, and the mechanical performance, the low-temperature resistance and the like of the sheath of the watertight cable are also superior to that of the existing watertight cable.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the true spirit and scope of the present invention, which is defined by the claims appended hereto. The techniques, shapes, and configurations not described in detail in the present invention are all known techniques.
Claims (8)
1. The utility model provides an anticorrosion acid and alkali-resistance watertight cable, a serial communication port, the cable includes many electrically conductive central unit, many electrically conductive central unit transposition stranding, and space department between the electrically conductive central unit all fills and blocks water and glue formation middle water blocking layer, many the outer cladding of electrically conductive central unit has the polyester layer, metal shielding layer and oversheath have set gradually outward outside the polyester layer, be provided with outer water blocking layer between oversheath and the metal shielding layer, the oversheath includes following weight part raw materials: 40-60 parts of chloroprene rubber, 20-25 parts of modified polytetrafluoroethylene, 16-18 parts of polyamide, 2-8 parts of nano silicon nitride, 3-5 parts of carbon nano fiber, 1-2 parts of zinc oxide, 1-2 parts of higher fatty alcohol, 0.5-1 part of calcium stearate and 3-4 parts of processing aid, wherein the modified polytetrafluoroethylene is prepared by compositely modifying polytetrafluoroethylene by tannic acid and trimesoyl chloride.
2. The anti-corrosion acid and alkali-resistant watertight cable according to claim 1, wherein the conductive central unit comprises a plurality of stranded conductors and an insulating layer wrapped outside the plurality of conductors, and a semi-conductive water-blocking glue is filled between the plurality of conductors to form an inner water-blocking layer.
3. The anti-corrosion acid and alkali-resistant watertight cable according to claim 2, wherein the metal shielding layer is braided by annealed copper wires, and the braiding density is 82% -83%.
4. The anti-corrosion acid and alkali resistant watertight cable according to claim 3, wherein the semiconductor water-blocking glue comprises the following raw materials in parts by weight: 100 parts of two-component silicon rubber, 20-28 parts of silicon resin, 10-16 parts of composite conductive particles, 4-6 parts of chlorinated paraffin, 2-3 parts of N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane and 1-2 parts of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
5. The anti-corrosion acid and alkali resistant watertight cable according to claim 4, wherein the composite conductive particles are core-shell structures in which CoP quantum dot/conductive carbon black composite particles are used as cores and polyaniline shell layers are wrapped outside the cores.
6. The preparation method of the corrosion-resistant, acid and alkali-resistant watertight cable according to any one of claims 2 to 5, wherein the preparation method specifically comprises the following steps:
stranding: twisting a plurality of required conductors, coating semiconductor water-blocking glue on the conductors while twisting, filling the semiconductor water-blocking glue in gaps among the conductors, and obtaining an internal water-blocking layer after solidification;
insulation: extruding an insulating layer on the surfaces of the conductors to obtain a conductive central unit;
cabling: taking the required conductive central units, stranding and cabling in a right-direction cabling direction in a layered stranding mode, simultaneously lapping polyester tapes to the left outside the plurality of conductive central units to form a polyester layer, and filling water-blocking glue behind each stranding cage in a stranding process to form a middle water-blocking layer;
weaving a metal shielding layer: weaving a soft copper wire outside the polyester layer to obtain a metal shielding layer, and coating a water-blocking adhesive on the metal shielding layer to form an outer water-blocking layer;
molding: and extruding and coating the smelted outer sheath raw material outside the outer water-blocking layer by using an extruding machine to obtain the watertight cable.
7. The preparation method of the corrosion-resistant, acid-and alkali-resistant and watertight cable according to claim 6, wherein the outer sheath is refined from the following raw materials: putting nano silicon nitride, carbon nanofiber and zinc oxide into a ball mill, ball-milling and uniformly mixing for 30-40min, adding absolute ethyl alcohol, carrying out ultrasonic oscillation for 10min, centrifuging and drying to obtain mixed granules, adding chloroprene rubber, modified tetrafluoroethylene and polyamide into an internal mixing furnace, heating to 150-180 ℃ within 30-45s, carrying out internal mixing for 30min, heating to 240-260 ℃ within 45-60s, carrying out internal mixing for 45min, cooling to 100-105 ℃ within 120-150s, adding the mixed granules, carrying out mixing for 20-30min, adding higher fatty alcohol, calcium stearate and a processing aid, heating to 135-150 ℃ and carrying out internal mixing for 10-15min, and discharging.
8. The preparation method of the corrosion-resistant, acid-and alkali-resistant, watertight cable according to claim 7, wherein the preparation method of the modified polytetrafluoroethylene comprises the following steps: adding sodium bicarbonate into deionized water, stirring to dissolve completely, adding Tween 80, stirring uniformly, adding tannic acid, magnetically stirring until the sodium bicarbonate is dissolved completely to obtain a tannic acid mixed solution, weighing trimesoyl chloride, adding the trimesoyl chloride into a normal hexane solution, carrying out ultrasonic oscillation for 30min, standing to remove bubbles to obtain a trimesoyl chloride mixed solution, cleaning polytetrafluoroethylene with deionized water and absolute ethyl alcohol in sequence, drying, adding the cleaned polytetrafluoroethylene into the tannic acid mixed solution, soaking for 15min, taking out the polytetrafluoroethylene, immediately adding the cleaned polytetrafluoroethylene into the trimesoyl chloride solution, carrying out stirring reaction for 5min, centrifuging, drying with hot air, baking at the temperature of 60 ℃ for 30min, taking out the dried polytetrafluoroethylene, cleaning with deionized water, and drying.
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